Method of flame proofing carpets

ABSTRACT

A novel method for flame proofing a carpet is disclosed which is based on the use of an aqueous composition that contains a foaming agent; a mixture of urea or thiourea and a polyhalo (Br, Cl) propanol ester of phosphoric, phosphoramidic or mixtures thereof; a water-soluble aminealdehyde resin, and an acid generating catalyst.

Unite States Patent 1191 Putnam et a1.

[ METHOD OF FLAME PROOFING CARPETS [75] Inventors: Robert C. Putnam,Mountain Lakes, N.J.; Jeffrey W. Young, Norristown,

[73] Assignee: Polaris Chemical Corp., Manville,

[22] Filed: Apr. 19, 1972 [21] Appl. No.: 245,672

Related U.S. Application Data [62] Division of Ser. No, 45,887, June 12,1970, Pat. No.

52 U.S. 0.... 117 137, 117/138.8 F, 117/138.8 N, 117/1388 UA, 117/141,117/143 A,

511 1111. c1. C09k 3/28, C09d 5/18 [58] Field of Search..117/137,'136,141, 117/1388 F, 138.8 UA, 143 A, 138.8 N;

106/15 PP; 260/294 R, 29.4 UA; 252/81; 161/403 [56] References CitedUNITED STATES PATENTS 3,047,425 7/1962 Hirshfeld et a1. 117/137 PrimaryExaminerWilliam D. Martin Assistant Examiner-Harry J. Gwinnell Attorney-George B. Finnegan et a1.

57 ABSTRACT A novel method for flame proofing a carpet is disclosedwhich is based on the use of an aqueous composition that contains afoaming agent; a mixture of urea or thiourea and a polyhalo (Br, Cl)propanol ester of phosphoric, phosphoramidic or mixtures thereof; awater-soluble aminealdehyde resin, and an acid generating catalyst.

-, 16 Claims, No Drawings METHOD OF FLAME PROOFING CARPETS This is adivision, of application Ser. No. 45,887, filed June 12, 1970, now US.Pat. No. 3,676,389.

BACKGROUND OF THE INVENTION.

This invention relates to flame-proofing compositions, Moreparticularly, it relates to aqueous flameproofing compositions capableof imparting effective flame-proofing properties to a carpet atunusually low concentrations.

Previous methods are known which impart flame retardation properties tovarious materials such as textiles, wood, etc. However, with respect toflameproofing textiles, and in particular carpeting, those methodsrequire the treated material to contain at least about a percent byweight increase in dry pick-up to render them effectively flameresistant. Furthermore, many of the previously used treatments whileproviding effective properties are not stable when subjected to awashing treatment.

The present invention is concerned primarily with flame-proofing ofcarpets. After a reasonable period of normal use, a carpet must becleaned and this usually entails some type of water wash or dry-foam ordry cleaning treatment. The soapy solution required to remove the spotsand stains from the carpet simultaneously acts in a detrimetnal mannerby entirely or partially removing the flame retardant material coated onthe carpet. As a result, one is left with a carpet which has lost asubstantial amount of its flame-proofing properties. It is apparent thatas further cleanings are carried out, more of the flame retardantcovering is lost.

It is, therefore, an object of this invention to furnish aflame-proofing composition which on application to a carpet provides ahighly advantageous flame-proofed carpet. It is a further object toprepare effectively flame-proofed carpets which contain unusually lowconcentrations of flame retardant added thereon. It is a further objectto prepare flame-proofed carpets which are capable of being washed underaqueous conditions repeatedly without the ensuing loss of flameretardation properties.

SUMMARY OF THE INVENTION foaming agent urea-ester mixture resin catalystEven more preferred is an aqueous composition as defined above whichcontains the following amounts of each component:

3.5 4.0% by weight 3.0%

foaming agent area-ester mixture resin catalyst Foaming agents which areadvantageously employed in the novel compositions of this inventioninclude ammonium salts, alkali halides and sulfamic acid. Illustrativeof these types of foaming agents are: ammonium bromide, diammoniumphosphate, ammonium sulfamate, ammonium chloride, ammonium thiocyanate,sodium bromide, potassium bromide, potassium chloride, lithium bromideand mixtures thereof.

Of particular preference is a 1:] parts by weight mixture of ammoniumbromide and diammonium phosphate and a 1:221 parts by weight mixture ofammonium bromide, diammonium phosphate and ammonium sulfamate.

The urea component of the urea-ester combination is preferably urea,however, thiourea can also be utilized to provide similar results.

As for the ester component, any polyhalo (Br, Cl) propanol ester ofphosphoric, phosphoramidic or phosphorodiamidic acid, phosphoramide,base-addition salts or mixture thereof is applicable for purposes ofthis invention. Particularly preferred esters include phosphoric acid,bis-(2,3-dibromopropyl)ester monoamrnonium salt; phosphoric acid,2,3-dibromopropyl ester monoammonium salt and phosphoric acid, 2,3-dibromopropyl ester diammonium salt.

The preferred amine-aldehyde water-soluble resins for inclusion into theabove-described aqueous compositions are illustrated by the following:ureaformaldehyde resin; melamine-glyoxal resin; guanidine-forrnaldehyderesin; and guanidine-glyoxal resin, melamine-formaldehyde; urea-glyoxaland combinations thereof.

The preferred acid generating catalysts for the aforedescribedcomposition are acid-addition salts of alkyl on hydroxy-alkylamines andacid salts of Group II elements. Typical examples include 2-methyl-2-aminopropanol hydrochloride, 4-aminobutanol hydrochloride,2-methyl-2-aminopropanol hydrobromide, n-propylamine hydrochloride,ethanolamine hydrochloride, zinc chloride and magnesium chloride.

Another preferred embodiment of this invention relates to a process fortreating carpeting with the aforedescribed aqueous solutions. Itconsists of flameproofing a carpet by impregnating it with the aforesaidcomposition until the dry add on is from 0.3% to about 10% by weight,drying and curing .the treated carpet. DETAILED DESCRIPTION OF THEINVENTION The novel aqueous compositions of this invention .may beapplied to textiles using conventional impregnation equipment andprocedures. Although this invention is concerned primarily with flameproofing of carpets, it may be used suitably for blankets, upholsteryand various fabrics as well.

Once treated with the compositions of this invention, the carpet willremain flame-proof even after numerous washings or shampooings. Moreimportantly, it will retain its flame retardant characteristics eventhough small amounts of flame retardant material have been used incoating the carpet.

The novelty of the herein described compositions resides in the uniquecombination of components which permit an unusually small amount ofadd-on on a textile thereby rendering it effectively fire-proof.

The material ingredients of the subject aqueous composition are:

a. a foaming agent,

b. a urea-ester mixture,

c. an amine-aldehyde resin and d. an acid-generating catalyst.

The aforesaid foaming agent is preferably an ammonium salt, an alkalihalide, sulfamic acid or mixtures thereof. More specifically, theammonium salt may be inorganic or organic, provided it is water-soluble.Suitable examples include ammonium bromide, ammonium phosphates,ammonium thiocyanates and ammonium acetate. Alkali halides which can beemployed include sodium bromide, potassium bromide and lithium bromide.Sulfamic acid is also an appropriate foaming agent.

It should be noted that combinations of the aforesaid materials aregenerally the most preferred situation. Moreover, in any given mixture,the amount of each component is not critical provided the amount of thetotal mixture is sufficient to comprise from 1 percent to about percentby weight of the aqueous composition.

Particularly effective combinations are:

ammonium bromide-diammonium phosphate (1:1 parts by weight) ammoniumbromide-diammonium ammonium sulfate (122:1 parts by weight) Theurea-ester component of the aforedescribed aqueous composition isanother integral part of the composition. The term urea is meant toinclude not only urea, but also thiourea and their water solublederivatives. Urea and thiourea are monoacid bases and may easily beconverted to a monoacid salt. For example with an equimolar amount ofhydrochloric acid, the monohydrochloride salt is obtained. These acidsalts are included within the purview of this application.

The amount of urea in the urea-ester mixture can range from as little as1 percent to as much as 50 percent by weight of the mixture.

The difference will consist of the ester component which is a polyhalo(Br, Cl) propanol ester or phosphoric, phosphoramide, base-additionsalts and mixtures thereof. Particularly suitable esters include:

phosphoric acid, bis-(2,3-dibromopropyl-ester, monoammonium saltphosphoric acid, 2,3-dibromopropyl ester, diammonium salt phosphoricacid, 2,3-dibromopropyl ester, monoammonium salt The base-addition saltis derived from a base which contains a suitable cation such as thealkali metal, alkaline earth metal, ammonium or water-soluble amineaddition salts like the lower alkanol-ammonium and other base salts withorganic amines. The conversion to baseaddition salts is astraightforward procedure. The base is treated with a substantiallyequimolar amount of a chosen base in an aqueous solution or in asuitable organic solvent such as methanol or ethanol.

It is obvious that for base-addition salt formations, a displaceablehydrogen ion must be available on the molecule. Accordingly, esters ofphosphorodiamidic acid and diesters of phosphoramide are not readilyconverted to base-addition salts.

The water-soluble amine-aldehyde resins which comprise another essentialingredient of the subject compositions are those prepared from an amineselected from urea, melamine or guanidine with an aldehyde selected fromformaldehyde and glyoxal. These resins are prepared by procedureswell-documented in the chemical phosphate literature. The ratio of amineto aldehyde is noncritical so long as the product is water soluble.Water solubility depends primarily on the number of methylol groups.

A preferred embodiment of the present invention is directed tocompositions which contain a greater amount of polyhalo ester thanamine-aldehyde resin.

The last essential ingredient of the hereindisclosed aqueous solution istermed an acid generating catalyst. By the term acid generating is meantthe ability to provide a protonic species. Examples of such materialsinclude acid addition salts of alkyl amines, hydroxy alkyl amines andacid salts of Group ll elements. Representative types areZ-methyl-Z-aminopropanol hydrochloride, zinc chloride and magnesiumchloride. Since this material acts as a catalyst, only small amounts arerequired in the composition. Most suitable is a range from 0.1 to 2percent by weight and most preferred is an amount of about 0.3 percentby weight.

The method by which the textiles, carpets, etc. become flame-proof isnot limiting: the composition can be applied using conventional textileimpregnation equipment and procedures. Suitable methods include bathtreatment, spray treatment, Kiss-Roll application and a combination ofspraying and drying of carpeting after it has been installed on floor orwall. However, many other suitable methods are also possible and arewithin the scope of the present invention. The flameproofingcompositions can be applied by a single treatment of a plurality oftreatments. The treatment is such that the resulting carpet or textileretains a dry add-on of from about 0.3 percent to about 10 percent byweight. After the wet treatment, the resulting material is dried andcured.

In addition to the four necessary components described above, thecomposition may also contain materials such as softening agents, dyes,wetting agents and the like which are nonreactive to the components ofthe flame-proofing compositions.

Carpets and textiles which are impregnated with the flame-proofingcompositions of this invention can suitably be dried and cured using theconventional textile drying and curing procedures and apparatus.

EXAMPLE I An aqueous composition containing the following ingredients isprepared:

water ammonium bromide diammonium phosphate urea phosphoric acid,bis-(2,3-dibromopropyl) ester, monoammonium salt melamine-formaldehyderesin Z-methyl-Z-aminopropanol hydrochloride 9665 parts by weight 143parts by weight 143 parts by weight 71 parts by weight 143 parts byweight parts by weight 35 pans by weight FLAME-PROOFING TREATMENTtreated carpet is found to have a 2.25 percent by weight solids add-on.

WASHING TREATM ENT The treated carpet is subjected to a washingvtreatment comprising: immersion in a soap solution, kneading for 3minutes, hosing off with fresh water and drying. This sequence of stepsis repeated ten times. This washed product passes the U.S. GovernmentStandard for the Surface Flammability of Carpets and Rugs DOC FF l-70(Pill test).

EXAMPLE II The aqueous composition described in Example I is used totreat the following carpet samples:

a. a carpet made of polyacrylonitrile;

b. a carpet made of poly(l,4-cyclohexylene dimethylene)terephthalate;

c. a carpet made from cotton;

d. a carpet made from jute;

e. a carpet made of viscose-nylon (80120);

f. a carpet made of polyacrylonitrile-poly (ethylene terephthalate)(50:50); and

g. a carpet made of wool.

All samples show improvement in fire-retardancy. The improvement andpermanency achieved depends on several factors: construction of thecarpet; amount of dry add-on; curing effects; and test methods used.

EXAMPLE III The procedure of Example I is repeated except that theresulting carpet has the following dry add-on amounts:

0.3 percent by weight 0.75 percent by weight 1.5 percent by weight 3.0percent by weight 7.0 percent by weight 10.0 percent by weight Allsamples show improvement in fire-retardancy.

EXAMPLE IV The procedure of Example 1 is repeated wherein the aqueouscomposition has the following percent by weight amount of foaming agent,i.e., ammonium bromide-diammonium phosphate (1:1 parts by weight):

0.7 percent 1.0 percent 1.5 percent 2.0 percent 4.0 percent 6.0 percent7.5 percent 10.0 percent All samples show improvement infire-retardancy.

EXAMPLE V The procedure of Example I is repeated wherein the aqueouscomposition has the following percent by weight amounts or ureaestermixture, i.e., ureaphosphoric acid, bis-(2,3-dibromopropyl) estermonoammonium salt (1:2 parts by weight):

0.7 percent 1.0 percent 1.5 percent 3.0 percent 7.5 percent 10.0 percentAll samples show improvement in fire-retardancy.

EXAMPLE VI The procedure of Example I is repeated wherein the aqueouscomposition has the following percent by weight amounts ofmelamine-formaldehyde resin:

0.2 percent by weight 0.5 percent by weight 1.5 percent by weight 2.5percent by weight 5.0 percent by weight All samples show improvement infire-retardancy.

EXAMPLE VII EXAMPLE VIII An aqueous composition containing the followingingredients is prepared:

9325 pans by weight 240 parts by weight 240 parts by weight 120 parts byweight Water Ammonium romide Diammonium phosphate Urea Phosphoric acid,bis- (2,3-dibromopropyl)ester, monoammonium salt Melamine-formaldehyderesin Z-methyI-Z-aminopropanol hydrochloride 240 parts by weight 100parts by weight 35 parts by weight A dry wool carpet having a jutebacking is treated with the above aqueous solution by a sprayingtechnique carried out at a temperature of about F., followed bybacksizing and finally drying and curing at 270 F. The resulting woolcarpet has a dry add-on of 2.4 percent.

After being subjected to the washing treatment described in Example I,it was tested and found to pass the pill test.

Instead of the washing treatment, a separate sample of the treatedcarpet was given ten (10) commercial shampooings by the Dry Foamprocess. It is then found to pass the Pill Test.

EXAMPLE IX The procedure of Example VIII is repeated wherein thefollowing foaming agent comprising 4.0 percent by weight of the totalaqueous composition is used in place of ammonium bromide-diammoniumphosphate (1:1) with good results:

ammonium bromide-diammonium phosphateammonium sulfamate (1:2:1 parts byweight) EXAMPLE X The procedure of Example VIII is repeated except anequivalent amount of thiourea is used in place of urea in the aqueouscomposition. The resulting carpet treated therewith shows an improvmentin fireretardancy.

EXAMPLE XI The procedure of Example I is repeated wherein the followingesters, in equivalent amounts, are used in place of phosphoric acid,bis-(2,3- dibromopropyl)ester, monoammonium salt with good results:

phosphoric acid, bis(2,3-dibromopropyl)ester phosphoramide, bis(2,3-dibromopropyl)ester phosphoric acid, 2,3-dibromopropyl esterphosphoric acid, 2,3-dibromopropyl ester, monoammonium saltphosphoramidic acid, 2,3-dibromopropyl ester phosphoric acid,2,3-dibromopropyl ester, diammonium salt phosphoric acid,bis-(2,3-dibromopropyl)ester monoammonium salt-phosphoric acid, (2,3-dibromopropyl)ester, monoammonium salt (1:1)

phosphoramidic acid, 2,3-dibromopropyl ester, ammonium saltphosphordiamidic acid, 2,3-dibromopropyl ester phosphoric acid,bis(2,3-dichloropropyl)ester, monosodium salt phosphoric acid,monopotassium salt phosphoric acid, monocalcium saltbis(2,3-dibromopropyl)ester,

bis(2,3-dibromopropyl)ester,

EXAMPLE XII The procedure of Example I is repeated wherein the followingresins, in equivalent amounts, are used inplace of melamine-formaldehyderesin:

urea-formaldehyde resin urea-glyoxal resin melamine-glyoxal resinguanidine-formaldehyde resin guanidine-glyoxal resin urea-formaldehydeurea-glyoxal (1:1)

All samples show improvement in fire-retardancy.

Example XIII The procedure of Example VIII is repeated wherein thefollowing acid-generating catalysts, in equivalent amounts, are used inplace of 2-methyl-2- aminopropanol hydrochloride: 4

2-methyl-2-aminopropanol hydrobromide 4-aminobutanol hydrochloriden-propylamine hydrochloride ethanolamine hydrochloride zinc chloride.

magnesium bromide All samples show improvement in fire-retardancy.

What is claimed is:

1. A process for flame-proofing a carpet which comprises impregnatingsaid carpet with a dry add on of from 0.3 to 10 percent by weight of acomposition which comprises:

a. from 0.7 to about 10 percent by weight of a foam ing agent selectedfrom the group consisting of ammonium bromide, diammonium phosphate,ammonium sulfamate, ammonium chloride, ammonium thiocyanate, sodiumbromide, potassium bromide, potassium chloride, lithium bromide andmixtures thereof;

b. from 0.7 to 10 percent by weight of a urea-ester mixture wherein saidurea component is selected from the group consisting of urea andthiourea and said ester component is selected from the group consistingof phosphoric acid, bis-(2,3-

dibromopropyl) ester, monoammonium salt; phosphoric acid,2,3-dibromopropyl ester, diammonium salt; a mixture of phosphoric acid,bis-(2,3- dibromopropyl)ester, monoammonium salt and phosphoric acid,2,3-dibromopropyl ester, monoammonium salt (121 by weight); phosphoricacid, bis-2,3-dibromopropyl) ester;phosphoramide, bis(2,3-dibromopropyl)ester; phosphoric acid, 2,3- dibromopropyl ester;phosphoramidic acid, 2,3- dibromopropyl ester; phosphoramidic acid, 2,3-dibromopropyl ester, ammonium salt; phosphordiamidic acid,2,3-dibromopropyl ester; phosphoric acid, bis(2,3-dichloropropyl)ester,monosodium salt; phosphoric acid, bis(2,3- dibromopropyl)ester,monopotassium salt; phosphoric 1 acid, bis(2,3-dibromopropyl)ester,monocalcium salt; the amount of urea component in said ureaester mixtureranging from 1 to 50 percent by weight of said mixture;

. from 0.2 to about 5 percent by weight of a watersoluble amine-aldehyderesin selected from the group consisting of urea-formaldehyde,melamineglyoxal, guanidine-formaldehyde, guanidineglyoxal,melamine-formaldehyde and urea-glyoxal; and

d. from 0.1 to about 2 percent by weight of an acidgenerating catalystselected from the group consisting of 2-methyl-2-aminopropanolhydrochloride, 4-aminobutanol hydro-chloride, 2-methyl-2- aminopropanolhydrobromide, n-propyl-amine hydrochloride, ethanolamine hydrochloride,zinc chloride and magnesium chloride.

2. The process of claim 1 wherein said foaming agent is a mixture ofammonium bromide and diammonium phosphate.

3. The process of claim 1 wherein said catalyst is zinc chloride.

4.The process of claim 1 wherein the treating composition comprises:

a. about 3.5 percent by weight of a 1:1 parts by weight mixture ofammonium bromide and diammonium phosphate;

b. about 3 percent by weight of a 1:2 parts by weight mixture of ureaand phosphoric acid, bis-(2,3- dibromopropyl)ester, monoammonium salt;

c. about 1 percent by weight of a melamineformaldehyde water-solubleresin; and

(1. about 0.3 percent by weight of Z-methyl aminopropanol hydrochloride.

5. The process of claim 1 wherein said carpet is made from wool.

6. The process of claim 1 wherein said carpet is made from polyester.

7. The process of claim 1 wherein said carpet is made frompolyacrylonitrile.

8. The process of claim 1 wherein said carpet is made from cotton.

9. The process of claim 1 wherein said carpet is made from a bast fiber.

10. The process of claim 1 wherein said carpet is made from nylon fiber.

11. The process of claim 1 wherein said carpet is made from aviscose-nylon fiber which has an :20 ratio of viscose to nylon.

phosphoric acid, bis-(2,3-dibromopropyl) ester, monoammonium salt.

15. The process of claim 12 wherein said aminealdehyde water-solubleformaldehyde resin.

resin isa melamine- 16. The process of claim 12 wherein said catalyst ishyd 2-methyl-2-aminopropanol rochloride.

mg UNITED STATES PATENT 0mm;v

CERTIFICATE OF CORRECTION Patent No. 3,762,942 Dated O o r 2, 1973Inventor) Robert C. Putnam et a1 It is certified that error" appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 4, line 29, change "of" to ---or Column '6, line 32, change"romide" to breinide Column 3, line 25; change "sulfate" to sulfamateColumn 8, line 3, insert after the semicolon phosphoric acid, 2,3dibromopropyl ester, monoammonium salt Signed-and sea led this 28thday'of May 19m.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. I 'c MARSHALL DANN Commissioner of PatentsAttesting Officer

2. The process of claim 1 wherein said foaming agent is a mixture ofammonium bromide and diammonium phosphate.
 3. The process of claim 1wherein said catalyst is zinc chloride.
 4. The process of claim 1wherein the treating composition comprises: a. about 3.5 percent byweight of a 1:1 parts by weight mixture of ammonium bromide anddiammonium phosphate; b. about 3 percent by weight of a 1:2 parts byweight mixture of urea and phosphoric acid,bis-(2,3-dibromopropyl)ester, monoammonium salt; c. about 1 percent byweight of a melamineformaldehyde water-soluble resin; and d. about 0.3percent by weight of 2-methyl aminopropanol hydrochloride.
 5. Theprocess of claim 1 wherein said carpet is made from wool.
 6. The processof claim 1 wherein said carpet is made from polyester.
 7. The process ofclaim 1 wherein said carpet is made from polyacrylonitrile.
 8. Theprocess of claim 1 wherein said carpet is made from cotton.
 9. Theprocess of claim 1 wherein said carpet is made from a bast fiber. 10.The process of claim 1 wherein said carpet is made from nylon fiber. 11.The process of claim 1 wherein said carpet is made from a viscose-nylonfiber which has an 80:20 ratio of viscose to nylon.
 12. The process ofclaim 1 wherein said amine-aldehyde water-soluble resin is made from anamine such as urea, and an aldehyde such as formaldehyde.
 13. Theprocess of claim 12 wherein said foaming agent is a 1:1 parts by weightmixture of ammonium bromide and diammonium phosphate.
 14. The process ofclaim 12 wherein said urea-ester mixture is a 1:2 parts by weightmixture of urea and phosphoric acid, bis-(2, 3-dibromopropyl) ester,monoammonium salt.
 15. The process of claim 12 wherein saidamine-aldehyde water-soluble resin is a melamine-formaldehyde resin. 16.The process of claim 12 wherein said catalyst is2-methyl-2-aminopropanol hydrochloride.